CN104058396A - Method for preparing large-size high-quality graphene with controllable number of layers - Google Patents
Method for preparing large-size high-quality graphene with controllable number of layers Download PDFInfo
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Abstract
The invention discloses a method for preparing large-size high-quality graphene with controllable number of layers, wherein graphite powder or flake graphite is mainly adopted as a raw material. The method specifically comprises the steps of intercalating the graphite raw material by virtue of an intercalating agent to initially weaken the intercalation interaction force and obtain different orders of graphite intercalation compounds (GICs); soaking the GICs in an appropriate expander, and then under the case that an auxiliary agent is added or not, enabling the intercalation materials to be quickly reacted with the expander to release a gases to obtain highly expanded wormlike graphene aggregate and further to cause the distances among graphene lamellar layers to be increased; and after certain processing, peeling, and then repeatedly centrifuging and dispersing to obtain a graphene dispersion with different numbers of layers. According to the method disclosed by the invention, the intercalation-expansion-peeling process is involved, raw materials are cheap, the reaction process is simple and easily controlled, and the number of layers of graphene is precisely controlled; the obtained graphene lamellar layers have the advantages of few defects, large size, high conductivity, high yield and the like, the large-scale industrial production is easily implemented, and the problems of high cost, low productivity, poor quality, small size, uncontrollable number of layers and the like in an existing graphene preparation technology are solved.
Description
Technical field
The invention belongs to Graphene preparing technical field, relate to the controlled large size of a kind of number of plies, high-quality graphene preparation method, be specially that a kind of to take oxygenant and acid solution be intercalator, obtain the compound between graphite layers of different layers exponent number, then add the chemical reagent such as oxalic acid or hydrogen peroxide, make it to discharge gas with interlayer material generation vigorous reaction, strut graphene sheet layer, after mechanical treatment, realize graphite and peel off, obtain the method for the controlled high-quality graphene of the number of plies.
Background technology
2004, the Geim group of Britain Manchester university uses " micromechanical forces disintegrating method " to obtain New Two Dimensional atomic crystal---the Graphene of individual layer or thin layer first, this discovery has shaken scientific circles, and from then on Graphene becomes a study hotspot in materialogy and physics field.Graphene is that carbon atom is with sp
2the carbonaceous material of the tightly packed one-tenth individual layer of hydridization bi-dimensional cellular shape lattice, it is the thinnest in the world two-dimensional material, there is the excellent performance such as high conductivity, high-specific surface area, high strength and high electron mobility, in fields such as nano electron device, photoelectric device, gas sensor, matrix material, field emmision material and stored energies, have broad application prospects.
Performance and its number of plies close relation due to Graphene, individual layer and double-layer graphite alkene are zero gap semiconductors, the current carrier that only has two types, electronics and hole, and the Graphene of 3-10 layer has multiple carrier type, and its valence band and conduction band occur significantly overlapping, this will determine that it has different performances, thereby determines its Application Areas.Therefore,, in order to realize the commercial applications of Graphene, it is the key challenge that many research work face that low-cost, high yield is prepared the controlled high-quality graphene of the number of plies.
At present, the method for preparing Graphene mainly contains five kinds.(1) mechanically peel method, transfers on silicon chip after utilizing adhesive tape sticking graphite again.The graphene-structured that this method prepares is comparatively complete, and cost is low, but productive rate is low, is not suitable for scale operation.(2) chemical Vapor deposition process (CVD).The standby Graphene of this legal system has more complete crystalline structure, but cost is higher, and preparation technology requires harshness, is difficult to realize mass-producing.(3) epitaxial growth method.The graphene film that this method obtains is the most even, and energy large area deposition, but graphene platelet is difficult separated with SiC, and cost is higher, is not suitable for equally scale operation.(4) chemical synthesis.This method can accurately be controlled the laminated structure of Graphene, but synthetic route is complicated, and output is extremely low, is still not suitable for preparation in macroscopic quantity.(5) oxidation reduction process.This method is the method for present stage preparing in a large number Graphene.But the graphene-structured that this method obtains is easily destroyed, usually defectiveness, affects the conductivity of Graphene, and can cause environmental pollution in reduction process, has limited equally this method large-scale industrialization application.The preparation method > > (CN101993061A) of the high-quality graphene that Chinese patent < < number of plies is controlled, by degree of oxidation and the dissociation degree of regulation and control graphite, realizes the number of plies of Graphene and controls.But the mixed gas reduction-oxidation graphite at 300-1000 ℃ that adopts hydrogen and argon gas in this method, exists the recovery time long, high to equipment requirements, reaction danger and high in cost of production problem.Chinese patent < < controlled high-quality graphene > > (CN103342358A) of a large amount of numbers of plies of quick preparation adopts Hummers method, by regulating and controlling different centrifugal speeds and time, obtain the graphite oxide of different degree of oxidations, through vacuum microwave reduction, obtain the Graphene of the fluffy cotton-shaped corresponding number of plies again.This method is simple to operate, environmental protection, but the Graphene defect obtaining is larger, and electroconductibility significantly reduces.Therefore, develop a kind of extensive, low cost and simple and easy to control, the method for preparing in a large number the controlled high-quality graphene of the number of plies is imperative.
Summary of the invention
The object of the invention is to develop the controlled high-quality graphene preparation method of the number of plies of a kind of low cost, high yield.It is simple that the method has operating process, safety, and the advantage such as the Graphene quality making is high, and controllability is good, is applicable to scale operation, has prospects for commercial application widely.
The controlled high-quality graphene preparation method of the number of plies that the present invention proposes, concrete steps are as follows:
(1) Graphite Powder 99 or crystalline flake graphite are added in intercalator, stirring reaction 5 min-48 h at 10-130 ℃, water and acetone repeat washing and filtering, dry 2-24 h at 50-100 ℃, obtain the compound between graphite layers (GICs) of different rank; Wherein graphite raw material is of a size of 10 μ m-500 μ m, and the mol ratio of graphite and intercalator is 1:0.05-12,
(2) GICs of step (1) gained different rank is dropped into respectively in swelling agent, add or do not add auxiliary, at 20-100 ℃, soak 5 h-7 d, make interlayer material fully react and discharge gas with swelling agent or auxiliary, obtain the quasiflake graphite alkene aggregate of high level expansion, thereby expand the interfloor distance between graphene sheet layer;
(3) through step (2) gained Graphene aggregate in suitable treatment agent after any mode in ultrasonic, shearing or ball milled is processed, realization is peeled off, then repeated centrifugation obtains the high-quality graphene dispersing solution of the different numbers of plies; Wherein:
Described ultrasonic power is 50-1600 W, and ultrasonic time is 5 min-2 h;
Described shearing rotating speed is 10-28000 rpm, and shear time is 10 min-5 h;
Described rotational speed of ball-mill is 200-1600 rpm, and Ball-milling Time is 1 h-6 h;
Described centrifugal rotational speed is 500-12000 rpm, and centrifugation time is 5 min-1 h.
In the present invention, intercalator described in step (1) can be a kind of or arbitrary combination between them in chromium trioxide, ammonium persulphate, potassium bichromate, potassium permanganate, the vitriol oil, concentrated hydrochloric acid, concentrated nitric acid, perchloric acid, strong phosphoric acid or Glacial acetic acid, and the concentration of controlling the vitriol oil, concentrated hydrochloric acid, concentrated nitric acid, perchloric acid, strong phosphoric acid and Glacial acetic acid is 10-20 mol/L.
In the present invention, swelling agent described in step (2) can be one or more in hydrogen peroxide, oxalic acid, potassium oxalate, ammonium oxalate, sodium carbonate or sodium hydrogen carbonate solution, wherein GICs and swelling agent consumption are: 0.1 g GICs collocation 10-50 mL swelling agent, the concentration of the swelling agent aqueous solution is 0.1-10 mol/L.
In the present invention, auxiliary described in step (2) can be sodium hydroxide, potassium hydroxide, sodium-chlor, Repone K, Sodium Thiocyanate 99, N, N-dimethylethanolamine, tetrabutylammonium, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium lauryl sulphate, urea, choline, SPC-D, carbamide peroxide, the aqueous solution such as sodium peroxydisulfate, N, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP), a kind of in orthodichlorobenzene (o-DCB) or dimethyl sulfoxide (DMSO) (DMSO), wherein the concentration of auxiliary in swelling agent is 0.01-0.4 mol/L.
In the present invention, described in step (3), suitably treatment agent refers to N, a kind of in dinethylformamide, N-Methyl pyrrolidone, orthodichlorobenzene or dimethyl sulfoxide (DMSO), wherein controlling the concentration of quasiflake graphite alkene aggregate in treatment agent is 0.1-10 mg/mL.
In the present invention, described repeated centrifugation is in the subnatant of gained after processing, to add treatment agent, at the centrifugal 10-20 min of 8000-12000 rpm, after repeated centrifugation 3 times, in subnatant, add treatment agent, centrifugal 10-60 min under 300-1000 rpm, repeated centrifugation is also collected the upper strata liquid of final gained, until upper strata liquid is colourless.
Utilizing the high-quality Graphene number of plies that preparation method of the present invention obtains is 1-10 layer, and lamella area can reach 10-10000 μ m
2(major part is 500 μ m
2above), productive rate can reach 70 %-95 %, and graphite lattice integrity degree is high, more than specific conductivity can reach 1500 S/cm.
The present invention compared with prior art has following advantage:
(1) directly buy business level graphite raw material and use, raw material sources are extensive, with low cost.
(2) the present invention does not relate to the redox processes of graphite, does not need the strong reductant that uses toxicity larger, does not need to use pure hydrogen at high temperature to reduce yet, and safety, avoids the danger of blasting.
(3) the present invention's condition that expands is simple, does not need the high-temperature expansion conditions such as microwave reactor, retort furnace, and can expand equably, avoids causing the problem of non-homogeneous expansion because Rapid Thermal expands.
(4) stripping process of the present invention is gentle, is conducive to obtain large-sized Graphene, and destroys hardly the structure of Graphene, can farthest retain the character such as the structure of Graphene and self calorifics, electricity, mechanics.
(5) it is few that the Graphene that the present invention makes has defect, and degree of oxidation is low, and size is large, the advantage such as the high and number of plies of productive rate is controlled.
(6) reaction conditions of the present invention is gentle, do not relate to high-temperature high-voltage reaction, and operation is simple, energy consumption is low, low production cost, has the potentiality of good large-scale industrial application.
Accompanying drawing explanation
Fig. 1 is scanning electronic microscope (SEM) figure after graphite intercalation, after expansion.(a) be the SEM figure after graphite intercalation; (b) be the SEM figure after compound between graphite layers expansion.
Fig. 2 is the Raman spectrogram of 2 rank and 5 rank compound between graphite layers.
Fig. 3 is the optical microscope image after expanding.
Fig. 4 is the field emission scanning electron microscope figure after graphite is peeled off.
Fig. 5 is the transmission electron microscope figure after graphite is peeled off.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further elaborated.Following examples are intended to the present invention to understand, and summary of the invention itself is not done to any restriction.Should be appreciated that, one or more steps that the present invention mentions are not repelled before and after described combination step and are also had other method and step, or can also insert other method and step between these specifically mentioned steps.Should also be understood that these examples are only not used in and limit the scope of the invention for the present invention is described.Except as otherwise noted, the numbering of various method steps is only for differentiating the object of various method steps, but not for to limit the ordering of each method or to limit practical range of the present invention, the change of its relativeness or adjustment, under the condition without the change of essence technology contents, when being also considered as the enforceable category of the present invention.
Embodiment 1
By 1 g crystalline flake graphite, (particle diameter is 500 μ m, carbon content >95%), 5 g chromium trioxides and 0.6 g potassium permanganate are put into 100 mL single necked round bottom flask, then add 12 mL Glacial acetic acid (99.5%), under 45 ℃ of water bath condition after stirring reaction 2d, filter, water and acetone repeat to wash repeatedly, remove unreacted chromium trioxide, being placed in 65 ℃ of vacuum drying ovens dries, obtain the GICs on 5 rank, as shown in Figure 1a, its Raman spectrogram as shown in Figure 2.The I of GICs as can be seen from Figure 2
d/ I
gbe worth very littlely, illustrate that the defect of lamella is few, oxidisability is low.
Then, the GICs that gets 0.1 g 5 rank drops in 20 mL hydrogen peroxide (30%), under room temperature, reacts after 2d, can find that graphite is constantly expanding, and filters, and washing, obtains quasiflake graphite alkene aggregate.By the pattern of scanning electronic microscope and polarized light microscope observing dilator, as shown in Fig. 1 b, Fig. 3.
Finally, quasiflake graphite alkene aggregate is placed in to ultrasonic 30 min of 100 mL NMP water-bath, obtains black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.Get upper strata liquid and carry out field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) test, result as shown in Figures 4 and 5.The number of plies great majority of illustrative experiment gained Graphene are 5 layers, and lamella area can reach 1000 μ m
2above, productive rate is about 90%, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 2
By 1 g crystalline flake graphite, (particle diameter is 500 μ m, carbon content >95%) put into 100 mL twoport round-bottomed flasks with 17 g chromium trioxides, put up device for absorbing tail gas, then add 14 mL concentrated hydrochloric acids (38%), stirring reaction under 45 ℃ of water bath condition, and absorb tail gas with sodium hydroxide.After 2 d, filter, water and acetone repeat to wash repeatedly, remove unreacted chromium trioxide, are placed in 65 ℃ of vacuum drying ovens and dry, and obtain the GICs on 2 rank.
Then, the GICs that gets 0.1 g 2 rank drops in 20 mL hydrogen peroxide (30%), reacts after 2 d under room temperature, filters, and washing, obtains quasiflake graphite alkene aggregate.
Finally, quasiflake graphite alkene aggregate is placed in to ultrasonic 30 min of 100 mL NMP water-bath, obtains black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.。The number of plies major part of experiment gained Graphene is 2 layers, and lamella area can reach 1000 μ m
2above, productive rate is about 90%, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 3
By 1 g crystalline flake graphite, (particle diameter is 500 μ m, carbon content >95%) put into 100 mL single necked round bottom flask with 3 g chromium trioxides, then add 10 mL Glacial acetic acid (99.5%), 2 h reflux at 122 ℃, filter, water and acetone repeat to wash repeatedly, remove unreacted chromium trioxide, be placed in 65 ℃ of vacuum drying ovens and dry, obtain the GICs on 3 rank.
Then, the GICs that gets 0.1 g 3 rank drops in 20 mL hydrogen peroxide (30%), reacts after 2 d under room temperature, filters, and washing, obtains quasiflake graphite alkene aggregate.
Finally, quasiflake graphite alkene aggregate is placed in to ultrasonic 30 min of 100 mL NMP water-bath, obtains black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.The number of plies major part of experiment gained Graphene is 3 layers, and lamella area can reach 1000 μ m
2above, productive rate is about 90%, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 4
By 1 g crystalline flake graphite, (particle diameter is 500 μ m, carbon content >95%) put into 100 mL single necked round bottom flask with 5 g chromium trioxides, then add 50 mL Glacial acetic acid (99.5%), at 80 ℃, react 2 h, filter, water and acetone repeat to wash repeatedly, remove unreacted chromium trioxide, be placed in 65 ℃ of vacuum drying ovens and dry, obtain the GICs on 6 rank.
Then, the GICs that gets 0.1 g 6 rank drops in 20 mL hydrogen peroxide, reacts after 2 d under room temperature, filters, and washing, obtains quasiflake graphite alkene aggregate.
Finally, quasiflake graphite alkene aggregate is placed in to ultrasonic 30 min of 100 mL NMP water-bath, obtains black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.The number of plies major part of experiment gained Graphene is 6 layers, and lamella area can reach 1000 μ m
2above, productive rate is about 90 %, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 5
By 1 g crystalline flake graphite, (particle diameter is 500 μ m, carbon content >95 %), 5 g chromium trioxides and 0.6 g potassium permanganate are put into 100 mL single necked round bottom flask, then add 12 mL Glacial acetic acid (99.5 %), under 45 ℃ of water bath condition, after stirring reaction 2 d, filter, water and acetone repeat to wash repeatedly, remove unreacted chromium trioxide, be placed in 65 ℃ of vacuum drying ovens and dry, obtain the GICs on 5 rank.
Then, the GICs that gets 0.1 g 5 rank drops in 20 mL hydrogen peroxide (30%), adds 36 mg N, and N-dimethylethanolamine (99 %) reacts after 2 d under room temperature, can find the quickening of graphite expansion speed, obtains quasiflake graphite alkene suspension.
Finally, by ultrasonic 10 min of quasiflake graphite alkene suspension water-bath, obtain black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.The number of plies great majority of experiment gained Graphene are 5 layers, and lamella area can reach 2000 μ m
2above, productive rate is about 90 %, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 6
The GICs that gets 0.1 g 5 rank drops in 20 mL hydrogen peroxide (30 %), adds 16 mg sodium hydroxide, reacts after 2 d under room temperature, can find the quickening of graphite expansion speed, obtains quasiflake graphite alkene suspension.
Then, by ultrasonic 10 min of quasiflake graphite alkene suspension water-bath, obtain black suspension, centrifugal 20 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 20 min of 12000 rpm, after repeated centrifugation 10 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, the number of plies great majority of experiment gained Graphene are 5 layers, lamella area can reach 2000 μ m
2above, productive rate is about 90 %, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 7
The GICs that gets 0.1 g 5 rank drops in 20 mL hydrogen peroxide (30 %), adds 0.5 mL TBAH (25 % in H
2o), under room temperature, react after 2 d, can find the quickening of graphite expansion speed, obtain quasiflake graphite alkene suspension.
Then, by ultrasonic 10 min of quasiflake graphite alkene suspension water-bath, obtain black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.The number of plies great majority of experiment gained Graphene are 5 layers, and dimensioned area can reach 2000 μ m
2above, productive rate is about 90 %, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 8
The GICs that gets 0.1 g 5 rank drops in 20 mL hydrogen peroxide (30%), adds 0.5 mL TBAH (25% in H
2o), under room temperature, react after 2 d, can find the quickening of graphite expansion speed, obtain quasiflake graphite alkene suspension.
Then, by quasiflake graphite alkene suspension Probe Ultrasonic Searching 10 min, obtain black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.The number of plies great majority of experiment gained Graphene are 5 layers, and dimensioned area can reach 500 μ m
2above, productive rate is about 90 %, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 9
The GICs that gets 0.1 g 5 rank drops in 20 mL hydrogen peroxide (30 %), adds 36 mg N, and N-dimethylethanolamine (99 %) reacts after 2 d under room temperature, can find the quickening of graphite expansion speed, obtains quasiflake graphite alkene suspension.
Then, rotating speed high speed shear 60 min by quasiflake graphite alkene suspension with 28000 rpm, obtain black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.The number of plies great majority of experiment gained Graphene are 5 layers, and dimensioned area can reach 5000 μ m
2above, productive rate is about 90 %, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 10
The GICs that gets 0.1 g 5 rank drops in 20 mL hydrogen peroxide, adds 36 mg N, and N-dimethylethanolamine (99 %) reacts after 2 d under room temperature, can find the quickening of graphite expansion speed, obtains quasiflake graphite alkene suspension.
Then, rotating speed ball milling 6 h by quasiflake graphite alkene suspension with 500 rpm, obtain black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.The number of plies great majority of experiment gained Graphene are 5 layers, and dimensioned area can reach 5000 μ m
2above, productive rate is about 90 %, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 11
Mix and blend 10 min under 5 ℃ of conditions by the 50 mL vitriol oils and 5 g ammonium persulphates, add 1 g crystalline flake graphite, 25
oin C water-bath, after continuously stirring 10 h, obtain the GICs on 1 rank.Then get 0.1 g GICs and slowly drop in 20 mL 0.1mol/L oxalic acid solutions, be transformed into rapidly the GICs on 2 rank, react after 2 d under room temperature, filter, washing, obtains quasiflake graphite alkene aggregate.
Finally, quasiflake graphite alkene aggregate is placed in to the ultrasonic 1h of 100 mL NMP water-bath, obtains black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.The number of plies great majority of experiment gained Graphene are 2 layers, and dimensioned area can reach 500 μ m
2above, productive rate is about 90 %, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 12
Mix and blend 10 min under 5 ℃ of conditions by the 50 mL vitriol oils and 5 g ammonium persulphates, add 1 g crystalline flake graphite, 25
oin C water-bath, after continuously stirring 10 h, obtain the GICs on 1 rank.Then get 0.1 g GICs and slowly drop in 20 mL 0.1mol/L oxalic acid solutions, add 36 mg N, N-dimethylethanolamine (99%), is transformed into rapidly the GICs on 2 rank, under room temperature, reacts after 2 d, obtains quasiflake graphite alkene suspension.
Then, rotating speed ball milling 3 h by quasiflake graphite alkene suspension with 500 rpm, obtain black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.The number of plies great majority of experiment gained Graphene are 2 layers, and dimensioned area can reach 5000 μ m
2above, productive rate is about 90 %, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Embodiment 13
Mix and blend 10 min under 5 ℃ of ice-water bath conditions by the 30 mL vitriol oils and 10 mL concentrated nitric acids, add 1 g crystalline flake graphite, 20
oin C water-bath, after continuously stirring 10 h, filter, obtain 1 rank GICs.
Then, get 0.1 g GICs and slowly drop in 20 mL 0.1 mol/L oxalic acid solutions, add 36 mg N, N-dimethylethanolamine (99 %) reacts 2 d under room temperature, can find the quickening of graphite expansion speed, obtains quasiflake graphite alkene suspension.
Finally, by ultrasonic 30 min of quasiflake graphite alkene suspension water-bath, obtain black suspension, centrifugal 10 min under 12000 rpm, remove upper strata liquid, add again NMP, at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm, repeated centrifugation is also collected upper strata liquid, until upper strata liquid is colourless.The number of plies great majority of experiment gained Graphene are individual layer, and dimensioned area can reach 1000 μ m
2above, productive rate is about 90 %, and the lattice perfection degree of Graphene is high, and defect is few, and specific conductivity can reach 2000 S/cm.
Comparative example 1
Get the 5 rank GICs that obtain in 0.1 g embodiment 1 and be placed in ultrasonic 30 min of 100 mL NMP water-bath, find that graphite is still particulate state, unsuccessful peeling off.
Comparative example 2
Get the 5 rank GICs that obtain in 0.1 g embodiment 1 and drop in 20 mL hydrogen peroxide (30 %), under room temperature, react after 2 d, can find that graphite, in continuous expansion, obtains quasiflake graphite suspension.Under 12000 rpm, centrifugal 10 min, remove upper strata liquid, then add NMP, and at centrifugal 10 min of 12000 rpm, after repeated centrifugation 3 times, lower floor adds NMP, centrifugal 30 min under 500 rpm.Find that graphite is still particulate state, upper strata liquid is colourless, and unsuccessful peeling off is described.
Comparative example 3
Get the 5 rank GICs that obtain in 0.1 g embodiment 1 and drop into 20 mL0.02 mol/L N, in N-dimethylethanolamine (99 %) aqueous solution, under room temperature, react after 2 d, can find that graphite major part is still sheet.By ultrasonic 2 h of mixed solution water-bath, obtain black suspension, in standing a moment, upper strata liquid is colourless, and unsuccessful peeling off is described.
Claims (6)
1. controlled large size, the high-quality graphene preparation method of the number of plies, is characterized in that concrete steps are as follows:
(1) Graphite Powder 99 or crystalline flake graphite are added in intercalator, stirring reaction 5 min-48 h at 10-130 ℃, water and acetone repeat washing and filtering, dry 2-24 h at 50-100 ℃, obtain the compound between graphite layers (GICs) of different rank; Wherein Graphite Powder 99 or crystalline flake graphite raw material are of a size of 10 μ m-500 μ m, and the mol ratio of Graphite Powder 99 or crystalline flake graphite and intercalator is 1:0.05-12;
(2) GICs of step (1) gained different rank is dropped into respectively in swelling agent, add or do not add auxiliary, at 20-100 ℃, soak 5 h-7 d, make interlayer material fully react and discharge gas with swelling agent or auxiliary, obtain the quasiflake graphite alkene aggregate of high level expansion, thereby expand the interfloor distance between graphene sheet layer;
(3) step (2) gained Graphene aggregate is in suitable treatment agent after any mode in ultrasonic shearing or ball milled is processed, and realization is peeled off, then by repeated centrifugation, obtains the high-quality graphene dispersing solution of the different numbers of plies; Wherein:
Described ultrasonic power is 50-1600 W, and ultrasonic time is 5 min-2 h;
Described shearing rotating speed is 10-28000 rpm, and shear time is 10 min-5 h;
Described rotational speed of ball-mill is 200-1600 rpm, and Ball-milling Time is 1 h-6 h;
Described centrifugal rotational speed is 500-12000 rpm, and centrifugation time is 5 min-1 h.
2. controlled large size, the high-quality graphene preparation method of a kind of number of plies according to claim 1, it is characterized in that, described intercalator refers to a kind of or arbitrary combination between them in chromium trioxide, ammonium persulphate, potassium bichromate, potassium permanganate, the vitriol oil, concentrated hydrochloric acid, concentrated nitric acid, perchloric acid, strong phosphoric acid or Glacial acetic acid; The concentration of controlling the vitriol oil, concentrated hydrochloric acid, concentrated nitric acid, perchloric acid, strong phosphoric acid and Glacial acetic acid is 10-20 mol/L.
3. controlled large size, the high-quality graphene preparation method of a kind of number of plies according to claim 1, is characterized in that, described swelling agent refers to one or more in hydrogen peroxide, oxalic acid, potassium oxalate, ammonium oxalate, sodium carbonate or sodium bicarbonate aqueous solution.
4. the controlled large size of a kind of number of plies according to claim 1, high-quality graphene preparation method, it is characterized in that, described auxiliary refers to sodium hydroxide, potassium hydroxide, sodium-chlor, Repone K, Sodium Thiocyanate 99, N, N-dimethylethanolamine, tetrabutylammonium, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium lauryl sulphate, urea, choline, SPC-D, carbamide peroxide, the aqueous solution such as sodium peroxydisulfate, N, dinethylformamide, N-Methyl pyrrolidone, a kind of in orthodichlorobenzene or dimethyl sulfoxide (DMSO), wherein the concentration of auxiliary in swelling agent is 0.01-0.4 mol/L.
5. controlled large size, the high-quality graphene preparation method of a kind of number of plies according to claim 1, it is characterized in that, described in step (3), suitably treatment agent refers to N, a kind of in dinethylformamide, N-Methyl pyrrolidone, orthodichlorobenzene or dimethyl sulfoxide (DMSO), controlling the concentration of quasiflake graphite alkene aggregate in treatment agent is 0.1-10 mg/mL.
6. controlled large size, the high-quality graphene preparation method of a kind of number of plies according to claim 1, is characterized in that, the prepared high-quality Graphene number of plies is 1-10 layer, and lamella area can reach 10-10000 μ m
2and major part is 500 μ m
2above, productive rate can reach 70 %-95 %, and graphite lattice integrity degree is high, more than specific conductivity can reach 1500 S/cm.
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